Treatment of textile materials



Patented Aug. 15, 1933 1,922,033 TREATMENT OF TEXTILE MATERIALS George Holland Ellis and William Bertram Miller, Spondon, near Derby, England, assignors to Celanese Corporation of America, a Corporation of Delaware Drawing. Application August 6,

Serial No. 383,977, and in Great Britain August 11 Claims.

The colouration of textile materials can be effected, as is known, by the oxidation thereon of variouspxidizable aromatic compounds, for example, aromatic bases such as p-amino-diphenylamine, a-naphthylamine, benzidine, or aniline, or mixtures thereof. In producing such colourations the material is usually padded or otherwise treated with a solution containing the aromatic compound and an oxidizing agent, the action or the latter being promoted by a subsequent ageing process.

Difiiculties have been experienced in the production of resist effects under such colourations by printing the material, after impregnating with the aromatic compound and oxidizing agent, with an alkali or a reducing agent to inhibit the action of the oxidizing agent on selected areas during a subsequent ageing or steaming process. Oxidation of the aromatic compound tends to occur prior to the application of the alkali or reducing agent with the result that the resisted portions are liable to be stained by the oxidation products.

It has been found that this tendency can be very much diminished or entirely avoided and that purer white or coloured resist effects can be produced with oxidation colourations on textile materials, and more particularly on materials made of or containing cellulose esters, for example cellulose acetate, or cellulose ethers, by ensuring that the oxidizable aromatic compound and oxidizing agent are never, even prior to the ageing process, present simultaneously on the parts of the material which are not to be coloured by the oxidation products of the oxidizable compounds.

According to the present invention therefore pattern effects are produced by the formation of oxidation colourations on materials, particularly materials made of or containing cellulose acetate or other cellulose esters or ethers, by a process comprising the separate operations of applying an agent adapted to inhibit oxidation to selected portions of the material, applying an oxidizing agent, and applying an aromatic com pound capable of yielding colourations by oxida tion, the oxidation inhibiting agent being applied before at least one of the other agents, and finally elfecting formation of said oxidation colourations.

The materials may, for example, be impregnated wholly or in part, for instance by padding or printing, with a solution of a suitable oxidizing agent for example a chlorate or a bichromate.

' A reducing agent may then be applied locally in the desired pattern by printing, stencilling, or otherwise, and the material then treated by padding or otherwise with a solution containinga suitable oxidizable aromatic compound or compounds, for example aromatic bases such as pamino-diphenylamine, a-naphthylamine, benzidine, or aniline. The material is finally subjected to steaming or ageing or other agency to develop the dyeing on those parts to which the oxidizing agent has been applied and has not been rendered inactive by the subsequent application of the reducing agent.

According to another method of carrying the invention into effect the materials may be treated locally in the desired pattern with the reducing agent prior to the application of the oxidizing agent, whereby the latter is rendered ineffective during the subsequent operations of applying and oxidizing the oxidizable aromatic compound. a

As reducing agent maybe used a hydrosulphite or an oxalate but it is preferred to use one which becomes active on ageing or steaming, for example sodium formaldehyde sulphoxylate, and to dry and age the fabric prior to treatment with the aromatic base or other oxidizable aromatic compound. The material may also be dried between other steps of the process. For application to cellulose ester or ether materials the aromatic amines or other oxidizable compounds may be employed in the form of their soluble salts or in the form of dispersions obtained in any convenient manner and with or without addition of alcohol or other substance having a swelling action on the cellulose derivative. Oxidation catalysts, for example salts of iron, copper, or vanadium, may be used in conjunction with the oxidizing agent, e. g. by incorporation in the solution of the oxidizing agent, or in the solution of the oxidizable aromatic compound or, in both. The oxidizing agents and/or reducing agents and/or oxidizable compounds may be applied to the materials in any convenient manner, and if desired or requisite in admixture with thickening agents. A comparatively small quantity of thickener may for example be added to solutions intended for application to the materials by padding but larger quantities may with advantage be added to preparations intended for application by printing.

Coloured resist effects maybe produced by incorporating in the reducing resist preparation dyestuffs, for example vat-dyestuffs, which are The invention is illustrated, but not limited, by the folowing examples:-

Example 1 A fabric woven from cellulose acetate yarns is impregnated in a suitable padding machine with a 5% solution of sodium chlorate and dried. It is then printed with a printing paste of the following composition:--

Grains Gum arabic 1:1 600 Water 180 Caustic soda 20 Sodium formaldehyde sulphoxylate 200 The printed fabric after drying is padded with the following liquor, being preferably passed direct to the squeezing rollers without previous immersion, the bottom roller running in the liquor.

Grams Paraaminodiphenylamine 150 Aniline 150 Methylated spirit 600 Glacial acetic acid 450 Lactic acid 50% 336 Cupric chloride 14 Gum arabic 1:1 900 Water 3600 The fabric is now dried and aged in the Mather Platt continuous ager at 100 C. or givenother similar suitable steaming after which it is washed well in warm water and finally soaped.

A white pattern on a black ground is obtained.

In a similar manner white patterns on a black ground may be produced on materials made of cellulose formate or cellulose propionate.

Example 2 A fabric woven from cellulose acetate yarns is impregnated with a 5% solution of sodium chlorate and is dried for printing. The chlorate prepared fabric is printed with a paste of the following composition:-

Grams Gum arabic 1:1 530 Ciba scarlet G 120 Caustic soda 10 Soda ash 10 Methylated spirit 50 Water 150 Hydrosulphite 30 Sodium formaldehyde sulphoxylate 100 Example 3 A fabric composed of cellulose acetate yarn is impregnated with a 5% solution of sodium dichromate and dried. It is then printed with a paste composed as follows:-

(minis Gum arabic 1:1 600 Water 180 Caustic soda 20 Sodium formaldehyde sulphoxylate 200 The printed fabric after drying is padded with the following liquor, being preferably passed direct to the squeezing rollers without previous immersion, the bottom roller running in the liquor.

Grams Paraphenylenediamine dissolved in 20 Water 700 Ammonium chloride dissolved in 20 Water 50 Sodium formaldehyde sulphoxylate 1.5

The padded material after drying is aged in the Mather Platt ager at 100 C. rinsed and finally soaped well.

A white pattern on a brown ground results.

Example 4 A woven fabric composed of cotton warp and cellulose acetate weft is padded in a 5% solution of sodium chlorate and dried. It is then printed with a printing paste of the following composition:

Grams Gum arabic 1:1 260 China clay; 100 Zinc formaldehyde sulphoxylate 200 Water 440 After drying the printed fabric is given a passage through the rapid ager or steamed in the cottage steamer for 3 minutes at 5 lbs. pressure and is then padded, preferably straight through the squeezing rollers with the following padding liquor:-

The fabric is dried and aged in the rapid ager at 100 C. or otherwise suitably steamed, washed in warm water and finally well soaped.

A white pattern on a black ground is obtained. Though the invention has been more particularly described with reference to the colouring of materials made of or containing cellulose acetate it is also applicable to the colouring of other materials, for example materials made of cotton or a regenerated cellulose type of artificial silk, or of other esters of cellulose, for example cellulose formate, propionate, or butyrate, or the products obtained by the treatment of alkalized cellulose with esterifying agents (e. g. the product known as immunized cotton obtained with p-toluenesulphochloride), or of cellulose ethers, for instance methyl, ethyl, or benzyl cellulose or the corresponding condensation products of cellulose and glycols or other polyhydric alcohols, or made of mixtures of two or more of these products.

What we claim and desire to secure by Letters Patent is:

l. A process for the production of coloured pattern effects on materials by the formation of oxidation colourations thereon, comprising the separate operations of applying an agent adapted to inhibit oxidation of the color-forming compound to selected portions of the material, of applying an oxidizing agent, and of applying an aromatic compound capable of yielding colourations by oxidation, the oxidation inhibiting agent being applied before at least one of the other agents, and finally effecting formation of said oxidation colourations.

2. A process for the production of coloured pattern effects on materials by the formation of oxidation colourations thereon, comprising the separate operations of applying a reducing agent to selected portions of the material, of applying an oxidizing agent, and of applying an aromatic compound capable of yielding colourations by oxidation, the reducing agent being applied before at least one of the other agents, and finally effecting formation of said oxidation colourations.

3. A process for the production of coloured pattern effects on materials by the formation of oxidation colourations thereon comprising applying an oxidizing agent, applying a reducing agent locally, applying an aromatic compound capable of yielding colourations by oxidation, and cansing the oxidizing agent to effect formation of said oxidation colourations.

4. A process for the production of colored pattern effects on materials by the formation of oxidation colorations thereon, comprising applying an oxidizing agent, applying a reducing agent locally, applying an aromatic amine capable of yielding colorations by oxidation, and causing the oxidizing agent to effect formation of said oxidation colorations.

5. A process for the production of colored pattern effects on materials, made of or containing cellulose acetate, by the formation of oxidation colorations thereon, comprising applying an oxidizing agent, applying locally a reducing agent in admixture with a coloring matter capable of being fixed on the material, applying an aromatic compound capable of yielding colorations by oxidation, and causing the oxidizing agent to effect formation of said oxidation colorations.

6. A process for the production of colored pattern effects on materials made of or containing organic derivatives of cellulose, by the formation of oxidation colorations thereon, comprising the separate operations of applying a reducing agent to selected portions of the material, of applying an oxidizing agent, and of applying an aromatic compound capable of yielding colorations by oxidation, the reducing agent being applied before at least one of the other agents, and finally effecting formation of said oxidation colorations.

'7. A process for the production of colored pattern effects on materials, made of or containing organic derivatives of cellulose, by the formation of oxidation colorations thereon, comprising applying an oxidizing agent, applying a reducing agent locally, applying an aromatic compound capable of yielding colorations by oxidation, and causing the oxidizing agent to effect formation of said oxidation colorations.

8. A process for the production of colored pattern effects on materials made of or containing cellulose acetate, by the formation of oxidation colorations thereon, comprising the separate operations of applying a reducing agent to selected portions of the material, of applying an oxidizing agent, and of applying an aromatic compound capable of yielding colorations by oxidation, the reducing agent being applied before at least one of the other agents, and finally eflecting formation of said oxidation colorations. t

9. A process for the production of colored pattern effects on materials made of or containing cellulose acetate, by the formation of oxidation colorations thereon, comprising applying an oxidizing agent, applying a reducing agent locally, applying an aromatic compound capable of yielding colorations by oxidation, and causing the oxidizing agent to effect formation of said oxidation colorations.

10. A process for the production of colored pattern effects on materials made of or containing cellulose acetate, by the formation of oxidation colorations thereon, comprising applying an oxidizing agent, applying a reducing agent locally, applying an aromatic amine capable of yielding colorations by oxidation, and causing the oxidizing agent to effect formation of said oxidation colorations.

11. A process for the production of colored pattern effects on materials made of of containing cellulose acetate, by the formation of oxidation colorations thereon, comprising applying an oxidizing agent, applying a reducing agent locally, applying a mixture of aniline and p-amino-diphenylamine, and causing the oxidizing agent to effect formation of said oxidation colorations.

GEORGE HOBLAND ELLIS. WILLIAM BERTRAM MILLER. 

